Photopolymerizable thermoplastics and methods of making and using same

Abstract

In one aspect, the disclosure relates to compositions comprising semicrystalline, linear photopolymers that possesses extraordinary mechanical properties for application in 3D printing. The photopolymers are rapidly fabricated using low viscosity liquids at ambient conditions.

What is claimed is: 
     
         1 . A thermoplastic polymer of formula (I-A): 
       
         
           
           
               
               
           
         
         wherein:
 each occurrence of Z is independently CH 2  or O; 
 each occurrence of A is independently absent or selected from the group consisting of (—CH 2 —) n5 , (—CH 2 —) n5 —O—C(═O)—, and (—CH 2 CH 2 O—) n5 ; 
 each occurrence of Q is independently absent, optionally substituted C 6 -C 18  arylene, or optionally substituted C 2 -C 15  alkylene; 
 each occurrence of X is independently selected from the group consisting of: 
 
       
       
         
           
           
               
               
           
         
       
       optionally substituted C 6 -C 18  arylene, optionally substituted C 2 -C 15  alkylene, 
       
         
           
           
               
               
           
         
       
       —O—, —S—, —S—S—, and 
       
         
           
           
               
               
           
         
         wherein:
 each instance of Y is independently O, C 6 -C 18  arylene, or C 6 -C 18  heteroarylene; 
 each instance of R′ is independently selected from the group consisting of optionally substituted C 1 -C 15  alkyl, optionally substituted C 1 -C 15  heteroalkyl, optionally substituted C 2 -C 15  alkenyl, optionally substituted C 2 -C 15  hetero alkenyl, optionally C 2 -C 15  alkynyl, optionally substituted C 2 -C 15  hetero alkynyl, optionally substituted C 5 -C 7  cycloalkyl, optionally substituted C 5 -C 7  heterocycloalkyl, optionally substituted C 6 -C 18  aryl, and optionally substituted C 6 -C 18  heteroaryl; 
 each instance of n is independently an integer from 2 to 200,000; 
 each instance of n1 is independently an integer from 0 to 25; 
 each instance of n2 is independently an integer from 0 to 25; 
 each instance of n3 is independently an integer from 0 to 25; 
 each instance of n4 is independently an integer from 1 to 12; 
 each instance of n5 is independently an integer from 1 to 10; and 
 wherein the thermoplastic polymer is semi-crystalline and has a melting point of about 70° C. to about 120° C. 
 
       
     
     
         2 . The thermoplastic polymer of  claim 1 , wherein X is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         3 . The thermoplastic polymer of  claim 1 , wherein Y is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         4 . The thermoplastic polymer of  claim 1 , wherein Y is O. 
     
     
         5 . The thermoplastic polymer of  claim 1 , wherein R′ is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         6 . The thermoplastic polymer of  claim 1 , wherein one of the following is true:
 n1 is 1 and n2 is 1;   n1 is 0 and n2 is 0;   each of n1 and n2 is independently 1, 2, 3, 4, or 5;   n3 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;   n4 is 1; or   n5 is 1 or 2.   
     
     
         7 . The thermoplastic polymer of  claim 1 , wherein the thermoplastic polymer is prepared from:
 a monomer of formula (II-A):   
       
         
           
           
               
               
           
         
         and 
         a monomer of formula (III-A): 
       
       
         
           
           
               
               
           
         
       
     
     
         8 . The thermoplastic polymer of  claim 7 , wherein the monomer of formula (II-A) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         9 . The thermoplastic polymer of  claim 7 , wherein the monomer of formula (III-A) is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         10 . The thermoplastic polymer of  claim 7 ,
 wherein the monomer of formula (II-A) is selected from the group consisting of   
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         and 
         wherein the monomer of formula (III-A) is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
       
     
     
         11 . The thermoplastic polymer of  claim 7 , wherein the thermoplastic polymer is crosslinked with a cross-linking agent. 
     
     
         12 . The thermoplastic polymer of  claim 11 , wherein the cross-linking agent is selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate) (TMPTMP), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO), 2,4,6-triallyloxy-1,3,5-triazine (TAT), triallyl trimellitate (TATM), and triallyl 1,3,5-benzenetricarboxylate (TABT).